1. Field of the Invention
This invention relates to oil soluble dispersant additives useful in fuel and lubricating oil compositions, including concentrates containing said additives, and methods for their manufacture and use. The dispersant additives are poly (C.sub.5 -C.sub.9 lactone) modified Mannich base adducts which are prepared from moieties of N-hydroxyaryl amine, di- or polyamine, high molecular weight hydrocarbyl-substituted dicarboxylic acid material, aldehyde and C.sub.5 C.sub.9 lactone. The high molecular weight hydrocarbon group has a number average molecular weight (M.sub.n) of about 700 to about 10,000. The additives will have a ratio (functionality) of about 0.70 to about 2.0 dicarboxylic acid producing moieties for each equivalent weight of the high molecular weight hydrocarbon therein.
2. Prior Art
It is known that polymers of 6 to 10 membered lactones such as valerolactone or epsilon-caprolactone, hereinafter E-caprolactone, can be prepared by reacting the lactone monomer with a hydroxyl or amine initiator. When reacting E-carprolactone, for example, the polymerization reaction may be illustrated by the following equations: ##STR1##
The reactions are known to be catalyzed by various esterification catalysts such as stannous octanoate, and a variety of different molecular weight products are feasible depending upon the ratio of lactone to initiator. Molecular weights on the order of from a few hundred up to about 5,000 are reproducably achievable.
Caprolactone can also be polymerized to a very high molecular weight, e.g., on the order of 100,000 or more. Typically such high molecular weight polymers do not employ initiators and preservation of functionality is not a requirement.
It is also known to react a lactone such as E-caprolactone with a diamine wherein one of the diamine groups is a tertiary amine and the other amine group is a primary or secondary amine to form a polycaprolactone polymer having a tertiary amine group at one end and a primary hydroxyl group at the other end. The polycaprolactone polymer would be used to neutralize polymeric acids.
U.S. Pat. No. 4,354,950 discloses a method of preparing Mannich base derivatives of hydroxyaryl succinimides of the formula ##STR2## where R is hydrocarbyl of 25 to 200 carbons, R' is H, alkyl or halogen, "n" is 2 or 3, "m" has a value of 1 to 5, Y is H or a methylene hydroxyaryl succinimide radical, "x" has a value of 1 to 2 when Y is H and a value of 1 when Y is a methylene hydroxyarl succinimide radical. The above succinimides are formed in a stepwise reaction, e.g., by reacting a polyalkenyl succinic anhydride with an aminophenol, to produce an intermediate N-(hydroxyaryl) hydrocarbyl succinimide, which is then reacted with an alkylene diamine or polyalkylene polyamine and an aldehyde (e.g., formaldehyde) in a Mannich base reaction to produce the described succinimides. The described succinimides may be added to a base oil of lubricating viscosity to form lubricant concentrates and lubricating oil formulations.
It has now been found that oil soluble dispersant additives, useful in fuel and lubricating oil compositions, including concentrates containing the additives, can be prepared by polymerizing a 6 to 10 membered lactone using as the initiator those lactone-reactive functions contained within the class of oil soluble Mannich base derivatives disclosed, for example, in U.S. Pat. No. 4,354.950.
While there are a number of prior art disclosures relating to Mannich base dispersants and to lactone polymerization reactions, in general, little or no prior art of direct pertinence appears to have surfaced in regard to the present dispersants. Exemplary of the patent literature which relates to lactone polymerization processes and/or to oil soluble dispersant additives are the following U.S. Patents: U.S. Pat. No. 4,362,635 discloses synthetic ester oils which are esterification products of monoalcohols and dicarboxylic acids or of polyhydric alcohols and monocarboxylic acids respectively, containing 5 to 45% by weight of units of hydroxycarboxylic acids obtained from aliphatic alcohols, aliphatic, cycloaliphatic or aromatic carboxylic acids, and lactones of aliphatic C.sub.5 -C.sub.12 hydroxycarboxylic acids. The synthetic ester oils are suitable for the preparation of lubricants and lubricant compositions.
U.S. Pat. No. 3,202,678 discloses as oil additives, N-polyamine substituted alkenyl succinimides, wherein the alkenyl radical is obtained by polymerizing a C.sub.2 -C.sub.5 olefin to form a hydrocarbon having a molecular weight ranging from about 400 to about 3000. The number of dicarboxylic acid producing moieties per hydrocarbon radical in the succinimides is not disclosed, but the mole ratio of polyolefin to maleic anhydride used to obtain the alkenyl succinimides is from 1:1 to 1:10.
U.S. Pat. No. 3,219,666 discloses as dispersing agents in lubricants, derivatives of polyalkenyl succinic acids and nitrogen compounds, including polyamines. The preferred molecular weight of the polyalkenyl moieties is 750-5,000.
U.S. Pat. No. 4,234,435 discloses as oil additives, polyalkylene substituted dicarboxylic acids derived from polyalkylenes having a M.sub.n of 1300 to 5,000 and containing at least 1.3 dicarboxylic acid groups per polyalkylene. In Example 34 of that patent, a polyisobutene-substituted succinic acylating agent is reacted with caprolactam in the presence of mineral oil and sodium hydroxide.
U.S. Pat. No. 3,381,022 relates to ester derivatives of substantially saturated polymerized olefin-substituted succinic acid wherein the polymerized olefin substituent contains at least about 50 aliphatic carbon atoms and as a molecular weight of about 700 to 5000. The esters include the acidic esters, diesters, and metal salt esters wherein the ester moiety is derived from monohydric and polyhydric alcohols, phenols and naphthols. The ester derivatives are useful as additives in lubricating compositions, fuels, hydrocarbon oils and power transmission fluids. A related application, i.e., U.S. Pat. No. 3,522,179, relates to lubricating compositions comprising a major amount of a lubricating oil and a minor proportion of an ester derivative of a hydrocarbon-substituted succinic acid sufficient to improve the detergency of the lubricating composition. The ester derivatives are similar to those described in U.S. Pat. No. 3,381,022 and contain at least about 50 aliphatic carbon atoms. The hydrocarbon substituent may be derived from a polymerized lower monoolefin having a molecular weight of from about 700 to about 5,000.
U.S. Pat. No. 4,502,970 discloses lubricating oil compositions useful in both gasoline engines and diesel engines. The compositions contain a polyisobutenyl succinicimide as a supplemental dispersant-detergent in combination with another conventional dispersant. The polyisobutenyl group has a M.sub.n of about 700-5,000.
U.S. Pat. No. 4,379,914 and its continuation-in-part (U.S. Pat. No. 4,463,168) disclose the preparation of polycaprolactone polymers by reacting E-caprolactone with a diamine wherein one of the amine groups of the diamine is a tertiary amine and the other is a primary or secondary amine. The polycaprolactone polymers are disclosed as being useful for neutralizing certain sulfonic acid-containing polymers to form amine-neutralized sulfonated derivatives.
U.S. Pat. No. 3,169,945 discloses the preparation of lactone polyesters which are useful as plasticizers and as intermediates for preparing elastomers and foams. The polyesters can be prepared by reacting a lactone such as E-caprolactone with an initiator such as an alcohol, amine or amino alcohol.
U.S. Pat. No. 4,532,058 discloses as a motor oil dispersant, a spirolactone condensation product formed by heating alkenyl succinic anhydrides in the presence of a basic catalyst, and then heating the resulting bicyclic spirodilactone condensation product with a polyamine or polyamine alcohol. It should be emphasized that this patent describes the intermolecular decaboxylation of an alkenyl succinic anhydride at elevated temperatures to form a condensation product and carbon dioxide as a by-product. This prior art is not concerned with polymerizable lactones which are the subject of the instant invention.
U.S. Pat. Nos. 4,113,639 and 4,116,876 disclose an example of alkenyl succinic anhydride having a molecular weight of the alkenyl group of 1,300 and a Saponification Number of 103 (about 1.3 succinic anhydride units per hydrocarbon molecule). This alkenyl succinic anhydride may be reacted with polyamine and then boric acid (U.S. Pat. No. 4,113,639), or may be reacted with an amino alcohol to form an oxazoline (U.S. Pat. No. 4,116,876) which is then borated by reaction with boric acid.
U.S. Pat. No. 4,062,786 in Example 13 shows a polyisobutenylsuccinic anhydride of molecular weight of about 1300 and a Saponification Number of about 100 (about 1.25 succinic anhydride units per alkenyl group).
U.S. Pat. No. 4,123,373 in Example 3 shows a polyisobutenylsuccinic anhydride of about 1,400 molecular weight having a Saponification Number of 80 (about 1.07 succinic anhydride units per polyisobutylene units).
U.S. Pat. No. 3,442,808 relates to lubricating oil additives prepared by reacting alkenyl succinic anhydride with the Mannich condensation product prepared by condensing alkyl substituted phenol, formaldehyde and polyalkylene polymaine.
U.S. Pat. No. 3,649,229 relates to reaction products obtained from high molecular weight alkyl-substituted hydroxy aromatic compounds, amines and aldehydes, which are disclosed to be useful as detergency improvers for liquid hydrocarbon fuels.
U.S. Pat. No. 3,798,165 relates to oil soluble high molecular weight Mannich condensation products formed by reacting certain high molecular weight alkyl-substituted hydroxy aromatic compounds, with a compound containing at least a HN&lt;group (e.g., an alkylene polyamine) and an aldehyde (e..g, formaldehyde).
U.S. Pat. No. 4,338,471 discloses a process for preparing substituted carboxylic acids and their derivatives succinic anhydride in which the synthesis reaction is carried out at least partially thermally in the presence of a furan-type compound. A similar process is disclosed in U.S. Pat. No. 4,450,281 wherein an alkenylsuccinic anhydride is made from a hydrocarbon with at least two double bonds, such as an ethylene-propylene-butadiene terpolymer. The products of these patents are useful as viscosity index improvers.
U.S. Pat. No. 4,584,117 and its division (U.S. Pat. No. 4,624,681) disclose additives which are useful as dispersants in lubricating oils, gasolines, marine crankcase oils and hydraulic fluids. The additives are prepared by first reacting a polyamine with a cyclic carbonate to form an intermediate, followed by reaction of this intermediate with an alkenyl or alkyl succinic anhydride.
U.S. Pat. No. 4,585,566 relates to nitrogen-containing dispersant additives having at least one primary or secondary amine group which have been modified by treatment with a cyclic carbonate. Examples of the nitrogen-containing dispersants which are so modified include polyoxyalkylene polyamines, Mannich bases, borated Mannich bases and hydrocarbyl sulfonamides having at least one additional amino group.
U.S. Pat. No. 4,612,132 related additives which are useful as dispersants and lubricating oils, gasolines and the like. The additives polyamino alkenyl or alkyl succinimides which have been reacted with cyclic carbonates, linear mono- or polycarbonates, or chloroformate to introduce carbonate functionality.
U.S. Pat. No. 4,614,603 is directed to polyamino alkenyl or alkyl succinimides which have been modified by treatment with a thiolactam, lactam or thiolactone. The modified materials are useful as dispersants or detergents in lubricating oils.
U.S. Pat. No. 4,617,138 relates to polyamino alkenyl or alkyl succinimides which have been modified by treatment with a lactone to yield modified succinimides with a hydrocarbylcarbonylalkylene group. The modified succinimides are useful as dispersants in lubricating oils, gasolines, marine crankcase oils and hydraulic oils. The lactones which are disclosed as being suitable for treating the succinimides are limited to 2-hydrocarbylcarbonyl substituted lactones which may be prepared, for example, by reacting an ester and a lactone, such as gamma butyrolactone or valerolactone in the presence of an organic or inorganic base.
European Pat. No. 202,024 relates to additives which are useful as dispersants in lubricating oils and hydrocarbon fuels and which are obtained by treating polyamino alkenyl or alkyl succinimides with a cyclic carbonate, thiocarbomate, or dithiocarbomate.
U.S. Pat. No. 4,645,525 discloses polyamine alkenyl or alkyl succinimides which have been modified by treatment with a lactone to yield polyamino alkenyl or alkyl succinimides wherein one or more of the basic nitrogens of the polyamino moiety is substituted with a hydroxyalkylene carbonyl group. The additives so disclosed are useful as dispersants in lubricating oils, gasolines, marine crank case oils and hydraulic oils.
U.S. Pat. No. 4,647,390 relates to additives which are useful as dispersants and detergents in lubricating oils and fuels. The additives are polyamino alkenyl or alkyl succinimides wherein one or more of the amino nitrogens of the succinimide is substituted with ##STR3## wherein R.sub.4 is hydrocarbyl of from 1 to 30 carbon atoms; R.sub.5 is hydrocarbyl of from 2 to 30 carbon atoms or --R.sub.6 --(OR.sub.6).sub.p --, where R.sub.6 is alkylene of 2 to 5 carbon atoms and p is an integer from 1 to 100; and m is an integer of from 0 to 1.
U.S. Pat. No. 4,663,062 discloses polyaminoalkenyl or alkyl succinimides which have been modified by treatment with a compound of the formula: ##STR4## wherein W is oxygen or sulfur; X is oxygen or sulfur; R.sub.4 is an alkylene group of from 2 to 3 carbon atoms or an alkylene group of from 2 to 3 carbon atoms substituted with from 1 to 3 alkyl groups of from 1 to 2 carbon atoms each; and R.sub.5 is hydrogen or alkyl of from 1 to 20 carbon atoms. The modified polyamino alkenyl or alkyl succinimides possess dispersancy and detergency in lubricating oils and in fuels. Similar disclosures are contained in U.S. Pat. Nos. 4,666,459 and 4,666,460.
U.S. Pat. No. 4,668,246 relates to polyamino alkenyl or alkyl succinimides which have been modified by treatment with a lactone to yield polyamino alkenyl or alkyl succinimides wherein one or more of the basic nitrogens of the polyamino moiety is substituted with a hydrocarbylcarbonylalkylene group. The additives are useful as dispersants in lubricating oils, gasolines, marine crank case oils and hydraulic oils.
Additional exemplary prior art disclosures which are expressly incorporated herein by reference in their entirely are U.S. Pat. Nos.: 2,890,208; 3,087,936; 3,131,150; 3,154,560; 3,172,892; 3,198,736; 3,215,707; 3,231,587; 3,325,484; 3,269,946; 3,272,743; 3,272,746; 3,278,550; 3,284,409; 3,284,417; 3,288,714; 3,361,673; 3,390,086; 3,401,118; 3,403,102; 3,455,827; 3,562,159; 3,576,743; 3,632,510; 3,684,771; 3,792,061; 3,799,877; 3,836,470; 3,836,471; 3,838,050; 3,838,052; 3,879,308; 3,912,764; 3,927,041; 3,850,341; 4,110,349; 4,116,875; 4,151,173; 4,195,976; 4,517,104; 4,536,547; and Re. 26,330.